Herbicidal and/or fungicidal 5-polyhaloethylimino- and 5-polyhalovinylimino-2,4-imidazolidinediones

ABSTRACT

5-(1-HYDROXY-2,2,2-TRIHALOETHYLIMINO)-, 5-(1,2,2,2TETRAHALOETHYLIMINO)- AND 5-(POLYHALOVINYLETHYLIMINO)-2,4IMIDAZOLIDINEDIONES AND THEIR USE AS HERBICIDES AND FUNGICIDES.

United States Patent [I 1 Singer Dec. 9, 197 5 1 HERBICIDAL AND/0R FUNGICIDAL [58] Field of Search 424/273 S-POLYHALOETHYLIMINO- AND 5-POLYHALOVINYLIMINO-2,4- {56] References Cited IMIDAZOLIDINEDIONES Malcolm S. Singer, Richmond, Calif.

Chevron Research Company, San Francisco, Calif.

Filed: Mar. 27, 1974 Appl. N0.: 455,167

Related US. Application Data Continuation-impart of Seri No. 239.357, March 29, 1972, Pat. No. 3,822,282.

Inventor:

Assignee:

US. Cl 424/ 273; 71/92 Int. Cl. A01N 9/22 FOREIGN PATENTS OR APPLICATIONS 2,0l3,098 3/1970 France 260/3096 Primary ExaminerFrederick E. Waddell Attorney, Agent, or Firm-J. A. Buchanan, Jr.; John Stoner. Jr; Raymond Owyang [57] ABSTRACT 5-( l-hydroxy2,2.2-trihaloethylimin0)-, 5-( l,2,2,2-tetrahaloethy1imino)- and 5-(polyhalovinylethylimino)- 2,4-irnidazolidinediones and their use as herbicides and fungicides.

11 Claims, N0 Drawings HERBICIDAL AND/OR FUNGICIDAL S-POLYl-IALOETHYLIMINO- AND 5-POLYHALOVINYL]MINO-2,4-IMIDAZOLl- DINEDIONES CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of copending application Ser. No. 239,357, filed Mar. 29, 1972, now US. Pat. No. 3,822,282, the disclosure of which is incorporated herein by reference.

BACKGROUND OF THE lNVENTlON This invention relates to 5-imino2,4-imidazolidinediones and their use as herbicides and fungicides.

Canadian Patent No. 879,711, issued Aug. 31, 1971 to Malcolm 8. Singer, common assignee, discloses herbicidal 5-imino-2,4-imidazolidinediones wherein the nitrogen in the 1 position of the imidazolidinedione nucleus is substituted with an aryl radical, the nitrogen in the 3 position is substituted with an aliphatic radical and the imino group is optionally substituted with a carbamoyl or n-chloroacetylcarbamoyl radical.

DESCRIPTION OF THE INVENTION The imidazolidinediones of the invention are represented by the formula (1) wherein R and R independently are alkyl of l to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms, naphthyl, phenyl, phenyl substituted withfrom l to 4 halogens of atomic number 9 to 35 (fluorine, chlorine or bromine) or from 1 to 2 alkoxy groups of l to 4 carbon atoms, alkphenyl of from 7 to 12 carbon atoms, or alkphenyl of from 7 to 12 carbon atoms and substituted with from 1 to 4 halogens of atomic number 9 to 35 or from i to 2 alkoxy groups of l to 4 carbon atoms; and R is 1- hydroxy-2,2,2-trihaloethyl, l,2,2,2-tetrahaloethyl, trihalovinyl or dihalovinyl wherein the halogen is of atomic number l7 to 35 (chlorine or bromine).

Illustrative alkyl R and R groups are methyl, ethyl, isopropyl, n-propyl and n-butyl. Illustrative alkenyl R and R groups are allyl, 2-butenyl, and 3-pentenyl. lllustrative aromatic R and R groups are phenyl; alkphenyl groups such as tolyl, xylyl, p-ethylphenyl; and alkoxyand halo-substituted phenyl and alkphenyl such as Z-flurophenyl, 2-chlorophenyl, 3-chlorophenyl, 3- fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 2,4- difluorophenyl, 3,4-difluorophenyl, 2,4-dichlorophenyl, 3-bromophenyl, 3,5-difluorophenyl, 3,5- dichlorophenyl, 2-fluoro-4-methylphenyl, 2-methy1-4- chlorophenyl, 4-methoxyphenyl, 2,4-diethoxyphenyl, 2-butoxyphenyl, 2-propoxy-4-methylphenyl, 2-chloro- 4-methoxyphenyl, 2-chloro-4-methoxyphenyl. Illustrative'R groups are l-hydroxy-2,2,Z-trichloroethyl, lhydroxy-2,2,2-tribromoethyl, l-hydroxy-2-bromo-2,2- dichloroethyl, 1,2,2,2-tetrachloroethyl, l,2,2,2-tetrabromoethyl, l,2,2-trichloro-2-bromoethyl, trichlorovinyl, l,2-dichloro-2-bromovinyl, tribromovinyl, 2,2- dichlorovinyl, 2,2-dibromovinyl.

Representative imidazolidinediones of formula (I) are:

l-methyl-3-(4-fluorophenyl)-5-( l ,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione, l-ethyl-3-(2,4-difluorophenyl)-5-( l-hydroxy-2,2,2- trichloroethylimino)-imidazolidine-2,4-dione, l -propyl-3-tolyl-5-( l-hydroxyl-2,2,2-tribromoethylimino)-imidazolidine-2,4-dione, l-isopropyl-3-(3,5-dibromophenyl)-5-( l-hydroxy- 2,2,2-trichloroethylimino)-imidazolidine-2,4- dione, l-phenyl-3-methyl-5-( l ,2,2,2-tetrabromoethylimino)-imidazolidine-2,4-dione, l-(4-chlorophenyl )-3-ethyl-5-( l-bromo-2,2,2-trichloroethylimino)-imidazolidine-2,4-dione, l-(2,4-dichlorophenyl )-3-propyl-5-( l,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione, i-(2,4-dichlorophenyl)-3-propyl-5-( l ,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione, l-( 3,5-dichlorophenyl)-3-n-butyl-5-( l,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione, l-methyl-3-(2-fluorophenyl-S-( l ,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione, l-methyl-3-( 2-chlorophenyl)-5-( 1-hydroxy-2,2,2 -trichloroethylimino)-imidazolidine-2,4-dione, l-methyl-3-phenyl-5-( l-hydroxy-2,2,Z-trichloroethylimino)-imidazolidine-2,4-dione, l-methyl-3-(2,4-difluorophenyl)-5-( l-hydroxy- 2,2,2-trichloroethylimino)-imidazolidine-2,4- dione, l-(2-fluorophenyl)-3-methyl-5-(1,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione, l-(2-chlorophenyl)-3-methyl-5-(1,2,2-trichloro-2- bromoethylimino)-imidazolidine-2,4-dione, l-(2-bromophenyl)-3-methyl-5-( l-hydroxy-2,2-

dichloro-2-bromoethylimino)-imidazolidine-2,4- dione, l-(2,4-difluorophenyl)-3-methyl-5-( l ,2,2,2-tetrachloroethylimino)-irnidazolidine-2,4-dione, l-( 2-fluorophenyl )-3-methyl-5-(trichlorovinylimino)-imidazolidine-2,4-dione, 1-(4-chlorophenyl)-3-methyl-5-(trichlorovinylimino)-imidazolidine-2,4-dione, l-methyl-3-phenyl-5-(trichlorovinylimino)- imidazolidine-2,4-dione, l-(3,4-dichlorophenyl)-3-methyl-5-(dichlorovinylimino)-imidazolidine-2,4-dione, l -methyl-3-( 3,5-difluorophenyl)-5-trichlorovinylimino)-imidazolidine-2,4-dione, l-methyl-3-(4-bromophenyl)-5-(dibromovinylimino)-imidazolidine-2,4-dione, l-(4-methoxyphenyl)-3-methyl-5-( 1 ,2-dichloro-2- bromovinylimino)-imidazolidine-2,4-dione, l-methyl-3-( 3-methoxyphenyl)-5-( l -bromo-2,2- dichlorovinylimino)-imidazolidine-2,4-dione. Preferred compounds of formula (I) are those wherein one R or R group is alkenyl, naphthyl, phenyl, alkphenyl, alkoxyor halo-substituted phenyl or alkphenyl and the other R or R group is alkyl, especially methyl. Particularly preferred compounds of formula (I) are those wherein one R or R is halo-substituted phenyl or alkphenyl of l to 2 halogens of atomic number 9 to 17 and the other R or R is methyl. The imidazolidinediones of the invention where R is a l-hydroxy-2,2,2-trihaloethyl'group are prepared by reacting a S-iminoimidazolidine-Z,4-dione with a trihaloacetaldehyde according to the following equa tion (l):

W O C RN/ R'+HECX, RN R' (l) I ll .1. i 11......

wherein R and R have the same significance as previously defined and X is chloro or bromo. it is appreciated, of course, that the Ol l-CHCX. group is the group R of formula (1).

The S-iminoimidazolidine-Z,4-dione reactants (formula (II) are known compounds and are described in Canadian Patent No. 879,71 1, issued Aug. 31, 1971, to M. 8. Singer.

Suitable trihaloacetaldehyde reactants are trichloroacetaldehyde, dichlorobromoacetaldehyde and tribromoacetaldehyde.

The reaction depicted by equation (1 is conducted in an inert solvent or neat. Generally, stoichiometric amounts of imidazolidinedione and aldehyde are employed. The reaction is preferably catalyzed by a small amount of a strong inorganic acid, e.g., sulfuric or perchloric acid. The reaction temperature is generally in the range of about 20 to 100C. The reaction proceeds rapidly and is generally complete in a matter of minutes. Reaction times of from 30 seconds to hours are generally sufficient.

The imidazolidinediones of the invention wherein R is a 1,2,2,2-tetrahaloethyl group are prepared by reacting the hydroxyimidazolidinedione (represented by formula (lll)) either in purified form or in the reaction mixture of equation (I) with a thionyl halide according to the following equation (2):

(Ill) wherein R, R and X have the same significance as previously defined.

The reaction depicted by equation (2) is accomplished by using from one mol to an excess of as much as 20 mols of the thionyl halide per mol of the imidazolidinedione reactant (Ill). The reaction temperature suitably varies from 20 to 100C. and the reaction time suitably varies from i to 20 hours. if desired, the chloroor bromoimidazolidinedione (1V) can be prepared directly from the 5-iminoimidazolidinedione reactant (11), the aldehyde reactant and the thionyl halide reactant in the same reactor by the general procedure employed for the reaction depicted by equation (2).

The compounds of the invention wherein R is a 2,2- dihalovinyl or trihalovinyl group are prepared by dehalogenation or dehydrohalogenation of the tetrahaloethyl compound (IV), as depicted by reaction wherein R, R and X have the same significance as previously defined, and Y is X or hydrogen. It is appreciated, of course, that Y is X when reaction (3) depicts a dehydrohalogenation reaction and that Y is hydrogen when equation (3) depicts a dehalogenation reaction. The dehydrohalogenation reaction is conducted under very mild basic conditions by conventional procedures at a temperature of from about 0 to 30C. and for a reaction time of about 15 minutes to 2 hours. The dehalogenation reaction is conducted by reacting the tetrahaloethyl compound (IV) with zinc metal by conventional procedures, e.g., in inert solvent at 25 to 100C.

The preparation of the compounds of the invention are further illustrated by the following examples:

EXAMPLES EXAMPLE 1 Preparation of 1-phenyl-3-methyl-5-( l-hydroxy-l ,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione l-phenyl-3-methyl-5-iminoimidazolidine-Z,4-dione (15.0 g 0.074 mol) was slurried in 40 ml chloroform. Chloral (21.8 g 0.148 mol) was added directly to the slurry. Exothermicity raised the temperature 20C. The reaction mixture was momentarily homogeneous before an abundance of product precipitated. An additional 100 ml of chloroform was added at this point. After 0.5 hour the mixture was filtered. The filter cake was washed with chloroform and dried. The product melted at l30-133C.

Flemental analysis showed: %C, calc. 41.1, found 41.8; %l-l, calc. 2.9, found 2.8; %N, calc. 12.0, found 12.3; %Cl, calc. 30.3, found 30.6.

EXAMPLE 2 Preparation of 1-(2-fluorophenyl)-3-methyl-5-(1,2,2,2-tetrachloroethylimino)-imidazolidine-2,4-dione 1-( 2-fluorophenyl )-3 -methyl-5-iminoimidazoladine- 2,4-dione (10.0 g 0.045 mol) was slurried in ml of 1,2-dimethoxyethane. Chloral (13.4 g 0.090 mol) was added, followed by the addition of 10.8 g (0.090 mol) thionyl chloride. The reaction mixture became homogeneous as the temperature rose from the heat of reaction. Temperature was maintained at 35-45C. for one-half hour. Solvent was removed from the mixture and the residue was taken up in benzene. Filtration removed some high-melting white solids. l-lexane was added to precipitate the product, which was filtered and washed with ether. The product melted at l75l77"C.

Elemental analysis showed: %C, calc. 37.2, found 37.5; %H, calc. 2.1, found 1.9; %N, calc. 10.9, found 10.9; %Cl, calc., 36.6, found 36.3.

EXAMPLE 3 Preparation of l-(4-chlorophenyl)-3-methyl-5 trichlorovinylimino)- imidazolidine-2,4-dione l-(4-chlorophenyl)-3-methyl-5 l ,2,2,-tetrachloroethylimino)-imidazolidine-2,4-dione (10.0 g 0.025 mol) was slurried in 35 ml acetonitrile. As triethylamine (2.5 g 0.025 mol) was added, the mixture became homogeneous and turned yellow. A precipitate began forming very soon after the triethylamine was added. Two hours later the mixture was filtered. The solid was a water-soluble amine hydrochloride. The filtrate was taken up in 75 ml methylene chloride, washed once with 75 ml water and dried over anhydrous magnesium sulfate. After filtration and solvent removal, the residual oil crystallized. It was stirred in ethanol and filtered to give 5.0 g of a yellow solid, mp. l08l 10C.

Elemental analysis showed: %C, calc. 39.27, found 40.6; %1-l,calc. l.92,found 1.7; %N, calc. 11.45, found 11.7.

EXAMPLE 4 Preparation of 1-(2-f1uorophenyl)-3-methyl-5-dichloroviny1imino)- imidazolidine-2,4-dione A mixture of 5 g (0.012 mol) -l(2-fluorophenyl)-3- methyl-5-( l-bromo-2,2,2-trichloroethylimino imidazolidine-2,4-dione and 1.6 g (0.024 mol) zinc powder in ml dimethoxyethane was heated under reflux for 16 hours. The hot reaction mixture was filtered and the solvent removed by evaporation under reduced pressure. The residue was a yellow oil which crystallized from ethanol as a pale yellow powder, m.p. l35-l38C.

Elemental analysis showed: %C, calc. 45.6, found 45.0; %H, calc. 2.6, found 2.2; %CI, calc. 22.4, found 22.09, %N, calc. 13.29, found 13.4.

EXAMPLE 5 Preparation of l-allyl-3'methyl-5-(trichlorovinylimino)-imidazolidine-2,4-dione l-allyl-3-methyl-5-iminoimidazolidine-2 ,4-dione (20.0 g 0.12 mol) and 17.7 g (0.12 mol) chloral in 50 ml chloroform were stirred at 25C. for one-half hour. To the resulting solution was added 28.69 (0.24 mol) thionyl chloride. The temperature rose to 35C. and a precipitate formed. The reaction mixture was heated at 55C. for 2 hours, cooled and filtered. The filtrate was stripped to give 24 g of 1-allyl-3-methyl-5- l,2,2,2-tetrachloroethylimino)-imidazolidine-2,4- dione, as a yellow oil.

A 7.3 g (0.072 mol) sample of triethylamine was added to a stirred mixture of 24 g l-ally1-3-methyl-5- 1,2,2,Z-tetrachloroethylimino)-imidazolidine-2,4- dione (prepared above) and 60 ml acetonitrile. A precipitate formed. The reaction mixture was stirred for b hours and filtered. The filtrate was diluted with 60 ml methylene chloride, washed with water, dried over magnesium sulfate, and stripped to give the product as an orange oil. Thin-layer chromatography showed the product to be homogeneous.

Elemental analysis showed: %C, calc. 36.5, found 35.8; %H, 2.7, found 2.5; %Cl, calc. 35.9, found 35.5; %N, calc. 14.2, found 13.2.

Other compounds of the invention were prepared using the methods as described above. These compounds are tabulated in Table l.

UTILITY The imidazolidinediones of the present invention are, in general, herbicidal in both preand post-emergent applications. For pre-emergent control of undesirable vegetation, these imidazolidinediones will be applied in herbicidal quantities to the environment, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergent applications, the imidazolidinediones of the present invention will be applied directly to the foliage and other plant parts. Generally they are effective against weed grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.

The imidazolidinediones of the invention are particularly effective as pre-emergent herbicides.

Pre-emergent herbicidal tests on representative imidazolidinediones of the invention were made using the following method:

EXAMPLE 6 Pre-emergent Herbicide Test An acetone solution of the test imidazolidinedione was prepared by mixing 750 mg imidazolidinedione, 220 mg of a nonionic surfactant and 25 ml of acetone. This solution was added to approximately 125 ml of water containing 156 mg of surfactant.

Seeds of the test vegetation were planted in a pot of soil and the imidazolidinedione solution was sprayed uniformly onto the soil surface at a dose of mcgm/c. The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc., for a 3-week period. At the end of this period, the herbicidal effectiveness of the imidazolidinedione was rated based on the physiological observations. 0-to-l00 scale was used, 0 representing no phytotoxicity and 100 representing complete kill. The results are reported in Table I1.

When used as herbicides, the amount of imidazolidinedione administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application i.e., sheltered areas such as greenhouses as compared to exposed areas such as fields, as well as the desired type of control. For pre-emergent control of most plants, dosages in the range of about 0.5 to 20 lbs/acre will be used. Such administration will give a concentration of about 2 to 30 ppm imidazolidinedione distributed throughout 0.1 acre-foot. For post-emergent application, such as foliar spray application, compositions containing about 0.5 to 8 lbs. imidazolidinedione per 100 gal of spray will be used. Such application is equivalent to about 0.5 to 20 lbs imidazolidinedione per acre.

The herbicidal compositions of this invention comprise an herbicidal amount of one or more of the above-described imidazolidinediones intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent such as water or acetone or a solid. The solid may be in the form of dust, powder or granules. These compositions will usually also contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth medium or plant tissue and generally enhance their effectiveness. These compositions may also contain other pesticides, stabilizers, conditioners, fillers, and the like.

EXAMPLE 7 Fungus Spore Test l(2-fluorophenyl)-3-methyl-5-(1,2,2,2-trichlorovinylimino)-imidazolidine-2,4-dione and l-phenyl-3-methyl-5-( 1,2,2-trichlorovinylimino )-imidazolidine were tested for effectiveness against spores of Monilim'a fructicola by means of a variation of "The Standard Spore Slide Germination Method for Determining Fungicidal Activity, described in the American Phytopathological Society Journal, Vol. 33, 627-632 (1943). The method measures the fungitoxic activity of fungicidal chemicals, their activity being expressed in terms of percent inhibition of germination of fungus spores. The compounds tested were dissolved in acetone to a concentration of ppm. The solutions were pipetted into the wells of depression slides and allowed to dry. The wells were filled with a suspension of the fungus spores. The spores were then incubated in a moist chamber overnight. A group of 100 spores was examined and the number of spores germinated and not germinated was counted and recorded to show the biological activity in terms of the percent germination inhibition.

Both compounds tested showed 100% germination inhibition.

EXAMPLE 8 Tomato Early Blight l-tolyl-3-methyl-5-( trichlorovinylimino )-imidazolidine-2,4-dione was tested for the control of the tomato early-blight organism, Alternaria solani candidi'a. Tomato (v. Bonny Best) seedlings of 6 to 7 weeks old were used. The tomato plants were sprayed with a I00- ppm solution of the test compound in an acetone-andwater solution containing a small amount of a nonionic emulsifier. The sprayed plants were inoculated one day later with the organism, dried and maintained at (i0-80% relative humidity for about 12 days. Percent disease control was based on the percent disease development on untreated check plants. The test compound gave 86% disease control.

EXAMPLE 9 Celery Late Blight The celery late-blight tests were conducted using celery (Utah) plants ll weeks old. The celery late-blight organism was Septoria apii. The celery plants were sprayed with a ISO-ppm solution of the test compound mixed in an acetone-and-water solution containing a small amount of a nonionic emulsifier. The plants were then inoculated with the organism and placed in an environmental chamber and incubated at 66-68F. in 100% relative humidity for an extended period of time (approximately 48 hours). Following the incubation the plants were allowed to dry and then were maintained at a -80% relative humidity for approximately 14 days. The percent disease control provided by a given test compound is based on the percent disease reduction relative to untreated check plants. The results are reported in Table III.

EXAMPLE 10 Leaf Rust The leaf-rust test was made using pinto beans. The pathogen was Uronyces phaseoli tipica. The pinto-beam plants were sprayed with a 250-ppm solution of the test compound in an acetone-water mixture containing a nonionic emulsifier. The treated plants were inoculated thereafter with the pathogen and then incubated in an environmental chamber for approximately 20 hours at 100% relative humidity and a temperature of 6870F. The plants were then removed from the chamber, allowed to dry, and then maintained in a greenhouse at a 60-80% relative humidity. The rate of infection on the leaves was made after about 14 days. The percent disease control provided by a given test compound was based on the disease reduction relative to untreated check plants. The results are reported in Table IV.

When used as fungicides, the compounds of the invention are formulated and applied in fungicidal amounts by conventional art methods to fungi or hosts which are subject to fungus attack, especially vegetative hosts such as plants, plant seeds, etc. The amount used will, of course, depend upon several factors such as the host, the type of fungus, the particular imidazolidinedione, etc. The amount used will generally range from 2 to by weight.

The compounds of the invention are generally admixed with biologically inert liquids or solids in an amount from about 0.005 to weight Higher or lower amounts can be used to advantage. Preferably from I to 50 weight of the composition will be the imidazolidinedione. Typical of the liquid carrier which may be admixed with the imidazolidinediones of this invention include liquids such as acetone, water, kerosene, xylene, alcohols, alkylated naphthylene and glycols. Typical solids which may be incorporated with the imidazolidinediones include the natural clays such as kaolin clays and diatomaceous earth, synthetic fine silica, talc, pyrophyllite, etc.

Fungicida] formulations may also contain stabilizers, spreading agents, sticking agents, fillers, other compatible pesticides, and the like.

TABLE I Elemental Analysis, Melting Point Calculated Found Compound C. C H Cl N C H Cl N tethyl3-phenyl5-(lhydroxy-2.2.2-tril40-l45 42.8 3.3 29.2 ll.5 43.9 3.9 29.3 ll.8

chloroethyliminol'imidazolidine-l.4-dione LphenylJ-methyl-S-(l .2.2.2-tetrachloro l47- l 51 39.] 2.5 38.4 11.3 40.6 2.6 360 l l .7

cthyliminol-imidazolidine-2.4-dione H 2-fluorophenyl)-3-methyl-5-( l ,2,2-tril57- I60 9.26 9.0

chloro2-brornoethylirnino)-imidazo|idine- 2.4dione 1 1 TABLE ill b Compound Control |-allyl-3-methyl-5-(trichlorovinylimino)-imidazolidine- 37 2,4-dione l-lm-chlorophenyl)-3-methyLS-(trichloro-vinylimino) 7| imidazolidine-2,4-dione l-(p-chlorophenyl)-3-methyl-S-(trichloro-vinylimino)- 84 imidazolidine-2,4-dione methyl 3-phenyl-5-(trichlorovinylimino)- 84 imidazolidine-ZA-dione I -p-tolyl-3-methyl-5-(trichlorovinylimino)-imidazolidine- 8| 2.4-dione l-methyl3-m-tolyl-S-(trichlorovinylimino)- 80 imidazolidine-2A-dione l-methyl-3-m-chlorophenyl-S-(trichloro-vinylimino)- l imidazolidine-ZA-dione H3 .5-dichlorophenyl)-3-methyl-S-(trichlorovinyl)-2.4- 64 imidazolidine-ZA-dione l-methyl-3-phenyl-5-(l .2.2.L-Ietrachloro-ethylimino)- 39 imidazolidine-2.4-dione l-o-fluorophenyll -methy|5(2-bromol .2.2- 23 trichloroethylimino)-imidazolidine-2.4-dione 23 l p-tolyl-3-methyl-5-( l-hydroxy-2.2.2- l l lrichloroethy|imino)-imidazolidine-2.4- dione l-13.4dichlorophenyl)-3-methyl-5-( I 222- 50 tetrachloroethylimino)-imidazolidine- ZA-dione TABLE IV Compound Control lmethyl-3-phenyl-S-(l.2.2.2-tetrachloro- 44 ethylimino)-imidazolidine-2.4-dione l-o-fluorophenyl-3-methyl-5-( 1 -hydroxy- 23 2r2r2-trichloroethylimino)-imidazolidine-2,4-dione l-methyl 3-phenyl-5-(l-hydroxy-2,2.2-tri- 37 chloroethylimino)-imidazolidine-2.4-dione lphenyl-Z-methyLS-tl-hydroxy-2.2,2-tri- 39 chloroethylimino)-imidazolidine-2.4dione lethyl-3-phenyl-5-( l .2,2.2-tetrachloro- 29 ethylimino)-imidazolidine-2,4-dione What is claimed is:

l. A method of controlling fungi which comprises applying thereto a fungicidally effective amount of a compound of the formula wherein one of R or R independently is alkyl of from I to 4 carbon atoms, and the other R or R is alkenyl of 3 to 6 carbon atoms, naphthyl, phenyl, halo-substituted phenyl of from 1 to 4 halogens of atomic number 9 to 35, alkphenyl of 7 to 12 carbon atoms, or halo-substituted alkphenyl of 7 to 12 carbon atoms and of from 1 to 4 halogens of atomic number 9 to 35 or from 1 to 2 alkoxy of l to 4 carbon atoms; and R is l-hydroxy-2,2,Z-trihaloethyl, l,2,2,2- tetrahaloethyl, trihalovinyl or dihalovinyl wherein the halogen is of atomic number 17 to 35.

2. The method of claim 1 wherein R is trihalovinyl.

3. The method of claim 2 wherein one of R or R is alkyl and the other of R or R is alkenyl.

4. The method of claim 3 wherein R is allyl, R is methyl and R is trichlorovinyl.

5. A fungicidal composition comprising a fungicidally effective amount of the compound defined in claim 1 and a biologically inert carrier.

nyl.

7. The composition of claim 6 wherein one of R or R is alkyl and the other of R or R is alkenyl.

8. The composition of claim 7 wherein R is allyl, R is methyl and R is trichlorovinyl.

9. The method of claim 1 wherein R is l,2,2,2-tetrahaloethyl.

10. The method of claim 9 wherein R is l,2,2,2-tetrachloroethyl.

ll. l-hydroxy-2,2,2-trihaloethyl.

I I I I 6. The composition of claim 5 wherein R is trihalovi- UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,925,553

DATED INV ENTOR(S) MALCOLM S. SINGER It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, line 35, C should read C II II N--R N--R Col. 5, lines 65-66, "1/2 Hours" should read 1-1/2 Hours Claim 11 Col. 12, line 42, should read The method of Claim 1 wherein R is l-hydroxy-2,2,Z-trihaloethyl.

Signed and Scaled this twenty-ninth D3) of June 1976 {SHALL Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParems and Trademarks 

1. A METHOD OF CONTROLLING FUNGI WHICH COMPRISES APPLYING THERETO A FUNGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. The method of claim 1 wherein R5 is trihalovinyl.
 3. The method of claim 2 wherein one of R1 or R3 is alkyl and the other of R1 or R3 is alkenyl.
 4. The method of claim 3 wherein R1 is allyl, R3 is methyl and R5 is trichlorovinyl.
 5. A fungicidal composition comprising a fungicidally effective amount of the compound defined in claim 1 and a biologically inert carrier.
 6. The composition of claim 5 wherein R5 is trihalovinyl.
 7. The composition of claim 6 wherein one of R1 or R3 is alkyl and the other of R1 or R3 is alkenyl.
 8. The composition of claim 7 wherein R1 is allyl, R3 is methyl and R5 is trichlorovinyl.
 9. The method of claim 1 wherein R5 is 1,2,2,2-tetrahaloethyl.
 10. The method of claim 9 wherein R5 is 1,2,2,2-tetrachloroethyl.
 11. 1-hydroxy-2,2,2-trihaloethyl. 